EP3473610B1 - Method of purifying a fluorinated c2-c20 organic acid - Google Patents

Method of purifying a fluorinated c2-c20 organic acid Download PDF

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EP3473610B1
EP3473610B1 EP17813230.4A EP17813230A EP3473610B1 EP 3473610 B1 EP3473610 B1 EP 3473610B1 EP 17813230 A EP17813230 A EP 17813230A EP 3473610 B1 EP3473610 B1 EP 3473610B1
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fluorine
acid
phase
mass
sulfuric acid
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German (de)
French (fr)
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EP3473610A1 (en
EP3473610A4 (en
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Shuuji ITATANI
Mihoko Ohashi
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
    • C07C53/19—Acids containing three or more carbon atoms
    • C07C53/21—Acids containing three or more carbon atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation

Definitions

  • the present invention which is defined in the claims, relates to a method for producing a fluorine-containing C 2-20 -organic acid (also abbreviated as "C 2-20 -FOA" hereinafter) .
  • a C 2-20 -FOA is known and this fluorine-containing organic acid, in particular a C 2-8 -FOA, is used as an emulsifier, for example, for producing polymers by emulsion polymerization.
  • an emulsifier impurities such as water and others may be mixed depending on a production method and/or a manner of use of an emulsifier. In order not to have unintended effect on emulsion polymerization, it is preferable that an amount of impurities in an emulsifier is small. In addition, emulsifiers are relatively expensive, so it is desirable to collect them after use and reuse them.
  • JP-A-2010-65034 discloses that a mixture containing a fluorocarboxylic acid, which is one of emulsifiers, and water is dehydrated by contacting it with a concentrated sulfuric acid to obtain a dehydrated fluorocarboxylic acid solution, and then the dehydrated fluorocarboxylic acid solution is purified by distillation operation.
  • EP-A-2 321 248 discloses a process for preparing a fluorocarboxylic acid, comprising the steps of (i) removing from a mixture containing a fluorocarboxylic acid and water at least a part of said water to obtain a dehydrated fluorocarboxylic acid solution and (ii) purifying said dehydrated fluorocarboxylic acid solution by common means, such as distillation or crystallization.
  • EP-A-0 566 974 ( US 5,312,935 ) describes a process for the purification of an impure perfluorinated carboxylic acid, comprising oxidizing the impurities in a reaction mixture comprising ⁇ 9 wt.% of water, impure perfluorinated carboxylic acid and an oxidant, thereby purifying the acid, and isolating the resulting purified perfluorinated carboxylic acid.
  • a fluorine-free (or fluorine-non-containing) organic compound is mixed as an impurity in a C 2-20 -FOA.
  • a fluorine-free organic compound includes, for example, fluorine-free carboxylic acids, hydrocarbons and polyethers which can be used as dispersion stabilizers (stabilizing aids) in emulsion polymerization or for other purposes.
  • a fluorine-free organic compound is usually present as a trace component in a C 2-20 -FOA, it is difficult to separate by distillation operation. If a fluorine-free organic compound can be effectively removed from a C 2-20 -FOA, it is convenient, for example, because it can regenerate the spent C 2-20 -FOA as an emulsifier and reuse it as an emulsifier.
  • An object of the present invention is to provide a method which is possible to effectively remove a fluorine-free organic compound from a mixture containing a C 2-20 -FOA and a fluorine-free organic compound, in other words, to provide a method for producing a C 2-20 -FOA with reduced fluorine-free organic compound.
  • a further object of the present invention is to provide a novel composition, which can be obtained by such a method, comprising a C 2-20 -FOA.
  • a fluorine-free organic compound can be extracted from a C 2-20 -FOA phase into a concentrated sulfuric acid phase (or at least partially removed from a C 2-20 -FOA) by contacting a mixture containing a C 2-20 -FOA and a fluorine-free organic compound with a concentrated sulfuric acid in a state in which substantially no water or a very small amount of water is present.
  • the present inventors have completed the present invention.
  • the present invention provides a method for purifying a fluorine-containing C 2-20 -organic acid (A), comprising
  • this contacting is conducted such that an amount of water present in the concentrated sulfuric acid phase is ⁇ 10 mass% and thus the C 2-20 -FOA can be obtained in the form of the C 2-20 -FOA phase having a reduced content ratio of a fluorine-free organic compound compared with said mixture.
  • the C 2-20 -FOA is selected from fluorine-containing C 2-20 -carboxylic acids (C 2-20 -fluorocarboxylic acids) and salts thereof, and fluorine-containing C 2-20 -sulfonic acids (C 2-20 -fluorosulfonic acids) and salts thereof.
  • Examples of the C 2-20 -fluorocarboxylic acid include the compounds of formula (i): X-Rf-COOH (i) wherein X is H, F or Cl, Rf is linear or branched C 1-19 -fluoroalkylene, a C 1-19 -group having a monooxyfluoroalkylene group or a C 1-19 -group having a polyoxyfluoroalkylene group.
  • the linear or branched C 1-19 -fluoroalkylene group in the above-mentioned Rf group may be C a F b H 2a-b (wherein a is an integer of 1-19 and b is an integer of ⁇ 2a).
  • Examples of such a group include CF 2 , C 2 F 4 , C 3 F 6 , C 4 F 8 , C 5 F 10 , C 6 F 12 , C 7 F 14 , CHF, C 2 F 3 H, C 2 F 2 H 2 , C 2 FH 3 , C 3 F 5 H, C 3 F 4 H 2 , C 3 F 3 H 3 , C 3 F 2 H 4 , C 3 F 1 H 5 , C 4 F 7 H, C 4 F 6 H 2 , C 4 F 5 H 3 , C 4 F 4 H 4 , C 4 F 3 H 5 , C 4 F 2 H 6 , C 4 FH 7 , C 5 F 9 H, C 5 F 8 H 2 , C 5 F 7 H 3 , C 5 F 6 H 4 , C 5 F 5 H 5 , C 5 F 4 H 6 , C 5 F 3 H 7 , C 5 F 2 H 8 , C 5 FH 9 , C 6 F 11 H, C 6 F 10 H 2 , C 6 F 9 H 3 ,
  • Examples of the C 1-19 -group having a mono- or polyoxyfluoroalkylene group in the above-mentioned Rf group include the groups of the formulae: (CF 2 ) l -(CF 2 OCF 2 ) m -(CF 2 OCF(CF 3 )) n formula (a) (CF 2 ) l -(CHFOCF 2 ) m -(CF 2 OCF(CF 3 )) n formula (b) (CF 2 ) l -(CF 2 OCHF) m -(CF 2 OCF(CF 3 )) n formula (c) (CHF) l -(CF 2 OCF 2 ) m -(CF 2 OCF(CF 3 )) n formula (d) (CHF) l -(CHFOCF 2 ) m -(CF 2 OCF(CF 3 )) n formula (e) (CHF) l -(CF 2 OCHF) m -(CF 2 OCF(CF
  • X is H or F
  • Rf is a C 1-19 -group having a mono- or polyoxyfluoroalkylene group
  • Rf is a C 1-7 -group, particularly a C 1-6 -group, each having a mono- or polyoxyfluoroalkylene group.
  • the C 2-20 -fluorocarboxylic acid is a perfluorocarboxylic acid of the formula (i-a): X-Rf-COOH (i-a)
  • the number of carbon atoms is preferably 4-10, more preferably 5-8, and particularly preferably 6-8.
  • Examples of the salts of the fluorocarboxylic acid and the fluorosulfonic acid include a salt having a monovalent cation as a counter ion, for example, alkali metal salts such as potassium salts and sodium salts, ammonium salts and amine salts (for example, alkylamine salts such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine).
  • alkali metal salts such as potassium salts and sodium salts
  • ammonium salts and amine salts for example, alkylamine salts such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine.
  • the fluorine-free organic compound may be an organic compound containing no fluorine.
  • the fluorine-free organic compound include a fluorine-free C 1-50 -organic compound.
  • the C 1-50 -organic compound include at least one of a fluorine-free C 1-50 -carboxylic acid and derivatives thereof, a fluorine-free C 8-50 -hydrocarbon, a fluorine-free C 6-50 -phenol, a fluorine-free C 1-30 -alcohol, a fluorine-free C 8-50 -polyether and a fluorine-free C 10-20 -alkyl group-containing ionic compound.
  • the number of carbon atoms of the above organic compounds is preferably 10-40, more preferably 14-35.
  • the fluorine-free C 1-50 -carboxylic acid may have one or more carboxyl groups.
  • Examples of the derivative of the fluorine-free C 1-50 -carboxylic acid include a carboxylic acid ester and/or those having substituents such as hydroxy and alkoxy.
  • Examples of the fluorine-free C 1-50 -carboxylic acid and derivatives thereof include the followings:
  • the number of carbon atoms of the carboxylic acid and its derivative is preferably 1-30, more preferably 1-20.
  • Examples of the fluorine-free C 8-50 -hydrocarbon include a linear, branched or alicyclic and saturated or unsaturated C 8-50 -hydrocarbon.
  • the number of carbon atoms is more preferably 10-40, even more preferably 20-40.
  • a saturated C 20-40 -hydrocarbon is sometimes referred to as paraffin. Since paraffin generally has a molecular weight distribution and has a wide range of boiling points, it is extremely difficult to separate paraffin by distillation operation.
  • the fluorine-free C 6-50 -phenol may be a monovalent or polyvalent phenol compound.
  • Examples of the fluorine-free C 6-50 -phenols include phenol, di-t-butylphenol, cresol, naphthol, hydroquinone, catechol, resorcinol, pyrogallol, phloroglucinol and hexahydroxybenzene.
  • the fluorine-free C 1-30 -alcohol may be a monovalent or polyvalent alcohol compound.
  • Examples of the fluorine-free C 1-30 -alcohol include methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexane-1-ol, heptan-1-ol, octan-1-ol, nonan-1-ol, decane-1-ol, undecan-1-ol, dodecan-1-ol, tridecan-1-ol, tetradecan-1-ol, pentadecan-1-ol, hexadecan-1-ol, heptadecan-1-ol, octadecan-1-ol, nonadecan-1-ol, icosan-1-ol, heneicosan-1-ol, docosan-1-ol, tricosan-1-ol, tetracosan-1-ol
  • fluorine-free C 8-50 -polyether examples include the followings:
  • fluorine-free C 10-20 -alkyl group-containing ionic compound examples include the followings:
  • the fluorine-free organic compound is not limited thereto, and it may be any other appropriate fluorine-free organic compound which can be added (and/or can be mixed), for example, as a dispersion stabilizer (a stabilizing aid), a surfactant, a chelating agent, a plasticizer, an initiator, a polymerization inhibitor, a chain transfer agent, an adhesion preventing agent and a machine oil.
  • the content ratio of the fluorine-free organic compound in the mixture containing the C 2-20 -FOA and the fluorine-free organic compound may be, for example, ⁇ 1000 mass-ppm, particularly ⁇ 500 mass-ppm, ⁇ 200 mass-ppm, ⁇ 100 mass-ppm, ⁇ 50 mass-p, ⁇ 30 mass-ppm, ⁇ 20 mass-ppm, ⁇ 10 mass-ppm, and but not particularly limited, it may be, for example, in the range of > 0.1 mass-ppm.
  • the content ratio of the fluorine-free organic compound in the above-mentioned mixture may be, for example, > 0.1 to 100 mass-ppm, particularly 0.2-500 mass-ppm, 0.5-200 mass-ppm, 0.5-100 mass-ppm, 1-50 mass-ppm, 1-30 mass-ppm, 1-20 mass-ppm, 1-10 mass-ppm.
  • the mixture containing the C 2-20 -FOA and the fluorine-free organic compound may contain other component which is, for example, a concentrated sulfuric acid, water, an inorganic substance (for example, an inorganic acids, a metal, other inorganic compound or elemental substance) and divalent metal salt.
  • a concentrated sulfuric acid water
  • an inorganic substance for example, an inorganic acids, a metal, other inorganic compound or elemental substance
  • divalent metal salt divalent metal salt.
  • the content of water in the mixture containing the C 2-20 -FOA and the fluorine-free organic compound is appropriately selected, according to the specific operation of the contact, so as to satisfy the condition relating to the amount of water in the contacting described later.
  • the mixture containing the C 2-20 -FOA and the fluorine-free organic compound can be obtained by any suitable method, and, for example, it may be those derived from a reaction mixture after synthesizing the C 2-20 -FOA or those derived from a reaction mixture after using the C 2-20 -FOA for emulsion polymerization.
  • the mixture containing the C 2-20 -fluorocarboxylic acid and the fluorine-free organic compound includes a reaction mixture obtained by a reaction (synthesis reaction) which produces the corresponding fluorocarboxylic acid by hydrolyzing the C 2-20 -fluorocarboxylic acid fluoride, and a reaction mixture obtained by a reaction (regeneration reaction) which produces the corresponding fluorocarboxylic acid by acidifying the C 2-20 -fluorocarboxylic acid salt used in the emulsion polymerization.
  • derived means that it may be obtained by appropriately subjecting the reaction mixture to post-treatment such as filtration, washing, deionization, dehydration and purification.
  • the mixture containing the C 2-20 -FOA and the fluorine-free organic compound may be previously subjected to dehydration treatment.
  • the dehydration treatment By the dehydration treatment, the amount of water in the mixture can be reduced to a desired level (for example, to a substantially negligible level) so that it is possible to easily attain the condition relating to the amount of water in the contacting described later.
  • the dehydration treatment may be carried out in either a batch manner or a continuous manner.
  • the dehydration treatment can be carried out by washing a mixture containing a precursor of the above-mentioned "the mixture containing the C 2-20 -FOA and the fluorine-free organic compound" as well as water with a sulfuric acid aqueous solution having a sulfuric acid concentration of ⁇ 70 mass%.
  • the dehydration treatment can be carried out by, for example, contacting a mixture containing the C 2-20 -FOA, the fluorine-free organic compound and water with a sulfuric acid aqueous solution having a sulfuric acid concentration of ⁇ 70 mass%, for example ⁇ 80 mass%, particularly ⁇ 90 mass%, more particularly ⁇ 96 mass%, further particularly ⁇ 98 mass%, more further particularly ⁇ 99.9 mass%, or typically a concentrated sulfuric acid, and then causing phase separation into a C 2-20 -FOA phase (or an organic phase or a fluorous phase) and a sulfuric acid phase (it can be understood as an aqueous phase since water is more distributed to the sulfuric acid phase than the fluorine-containing organic acid phase) to obtain the above-mentioned "the mixture containing the C 2-20 -FOA and the fluorine-free organic compound" in the form of the C 2-20 -FOA phase.
  • a sulfuric acid aqueous solution having a sulfuric acid concentration
  • the sulfuric acid concentration means the sulfuric acid concentration of the sulfuric acid phase (the aqueous phase) during the dehydration treatment.
  • the amount ratio of the mixture containing the C 2-20 -FOA, the fluorine-free organic compound and water and the sulfuric acid aqueous solution is not particularly limited as long as the above sulfuric acid concentration can be maintained.
  • the mixture containing the C 2-20 -FOA, the fluorine-free organic compound as well as water is subjected to contacting with a sulfuric acid aqueous solution (particularly a concentrated sulfuric acid) for the purpose of dehydration, and then is subjected to contacting with a concentrated sulfuric acid for the purpose of extraction (reduction or removal) of the fluorine-free organic compound, which will be described later. Therefore in summary, it will be washed at least twice with a sulfuric acid (especially a concentrated sulfuric acid).
  • the contacting with a sulfuric acid aqueous solution for the purpose of dehydration may be carried out twice or more until the desired dehydration (water content) level is reached.
  • the dehydration treatment is not limited to washing with a sulfuric acid, but any other appropriate method, for example, which is carried out by contacting the mixture containing the C 2-20 -FOA, the fluorine-free organic compound and water with a water-absorbing substance such as diphosphorus pentaoxide or zeolite (in the presence or absence of the above-mentioned sulfuric acid aqueous solution).
  • a water-absorbing substance such as diphosphorus pentaoxide or zeolite (in the presence or absence of the above-mentioned sulfuric acid aqueous solution).
  • zeolite include aluminosilicate.
  • the water content of the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, which has been previously subjected to dehydration treatment is, for example, ⁇ 1.0 mass%, preferably ⁇ 0.7 mass%, particularly preferably ⁇ 0.2 mass%.
  • the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, as described above, is contacted with a concentrated sulfuric acid (hereinafter referred to as "extraction treatment of the fluorine-free organic compound").
  • (a) concentrated sulfuric acid refers to a sulfuric acid aqueous solution having a sulfuric acid concentration of ⁇ 90 mass%.
  • the sulfuric acid concentration of the concentrated sulfuric acid is, for example, ⁇ 92 mass%, particularly ⁇ 96 mass%, typically ⁇ 98 mass%.
  • the mass ratio (the flow ratio in the case of continuous manner) of the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, and the concentrated sulfuric acid is not particularly limited as long as it can satisfy the condition relating to the amount of water in the contacting described later. However, it can be, for example, 10:1 to 1:1, in particular 10:2 to 10:5.
  • the extraction treatment of the fluorine-free organic compound it is preferable to stir and mix the mixture containing the C 2-20 -FOA and the fluorine-free organic compound and the concentrated sulfuric acid so as to contact sufficiently with each other.
  • droplets of the C 2-20 -FOA phase can be dispersed as a dispersed phase in the concentrated sulfuric acid phase as a continuous phase.
  • the contacting of the mixture containing the C 2-20 -FOA and the fluorine-free organic compound with the concentrated sulfuric acid in the extraction treatment of the fluorine-free organic compound is conducted such that the amount of water present in the concentrated sulfuric acid phase is ⁇ 10 mass%.
  • the fluorine-free organic compound can be extracted from the C 2-20 -FOA phase into the concentrated sulfuric acid phase (or at least partially removed from the C 2-20 -FOA).
  • the(an) amount of water present in the concentrated sulfuric acid phase means the amount of water present in the concentrated sulfuric acid phase, before, during or after separating the C 2-20 -FOA phase.
  • the amount of water may be determined by calculation if possible (for example, wherein the concentrated sulfuric acid phase is considered to be substantially uniform irrespective of its part) or may be measured by directly analyzing the concentrated sulfuric acid phase sampled from any appropriate part of the apparatus performing the separation operation.
  • the outlet concentration obtained by sampling the concentrated sulfuric acid phase withdrawn from the outlet of the apparatus and measuring its amount of water can be set as "the amount of water present in the concentrated sulfuric acid phase", without problems.
  • the analysis can be carried out, for example, by Karl Fischer method.
  • the amount of water may be ⁇ 10 mass%, preferably ⁇ 8 mass%, particularly ⁇ 4 mass%, and more preferably ⁇ 2 mass%.
  • the C 2-20 -FOA can be obtained in the form of the C 2-20 -FOA phase having the reduced content ratio of the fluorine-free organic compound as compared with the original mixture (mixture containing the C 2-20 -FOA and the fluorine-free organic compound).
  • the fluorine-free organic compound does not need to be extracted into the concentrated sulfuric acid phase as it is, and the fluorine-free organic compound may be reduced or removed in the C 2-20 -FOA phase as compared with the original mixture.
  • the fluorine-free organic compound may be extracted in a state of being decomposed into the concentrated sulfuric acid phase.
  • the content ratio of the fluorine-free organic compound in the resulting C 2-20 -FOA phase is preferably, for example, ⁇ 0.1 mass-ppm, and particularly preferably ⁇ 0.05 mass-ppm.
  • the remainder of the C 2-20 -FOA phase is preferably composed of the C 2-20 -FOA.
  • the extraction treatment of the fluorine-free organic compound may be carried out in either a batch manner or a continuous manner.
  • the mixture containing the C 2-20 -FOA and the fluorine-free organic compound is thoroughly mixed with the concentrated sulfuric acid, and then the mixed solution is left to stand (for example, mixing is stopped after mixing for a predetermined time) to phase-separate into the targeted C 2-20 -FOA phase containing the C 2-20 -FOA and the concentrated sulfuric acid phase and collect the C 2-20 -FOA phase.
  • the resultant C 2-20 -FOA phase can be again mixed with a concentrated sulfuric acid, and then the mixture can be left to stand to obtain the C 2-20 -FOA phase having a smaller amount of the fluorine-free organic compound. This operation may be repeated until the concentration of the fluorine-free organic compound in the C 2-20 -FOA phase becomes lower than the desired level.
  • the extraction treatment of the fluorine-free organic compound may include a step of continuously contacting a C 2-20 -FOA phase and the concentrated sulfuric acid phase in a liquid-liquid heterophasic dispersion system consisting of the C 2-20 -FOA phase and the concentrated sulfuric acid phase and a step of phase-separating the C 2-20 -FOA phase and the concentrated sulfuric acid phase.
  • a static mixer 10 and a liquid-liquid separation column 20.
  • the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, and the concentrated sulfuric acid are supplied from any one and the other of supply ports 11 and 12 to the static mixer 10, respectively.
  • the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, and the concentrated sulfuric acid are stirred and mixed by passing through the static mixer 10 in which an element 13 is installed, and the extraction of the fluorine-free organic compound can occur continuously in the static mixer 10.
  • mixed solution is discharged from a discharge port 14, and then supplied to the liquid-liquid separation column 20.
  • the mixed solution supplied from the supply port 23 is liquid-liquid separated into a heavy liquid 21 and a light liquid 22 in the liquid-liquid separation column 20, and therefore the C 2-20 -FOA phase can be collected.
  • the correspondence relationship of the C 2-20 -FOA phase and the concentrated sulfuric acid phase with the heavy liquid and the light liquid is determined depending on the densities (or the specific gravities) of the C 2-20 -FOA phase and the concentrated sulfuric acid phase, and may vary depending on the type of the C 2-20 -FOA.
  • "the amount of water present in the concentrated sulfuric acid phase” is the amount of water present in the concentrated sulfuric acid phase withdrawn from the outlet of the liquid-liquid separation column 20.
  • It may be measured by directly analyzing the concentrated sulfuric acid phase sampled from the outlet of the apparatus, or may be calculated from respective moisture contents of the mixture containing the C 2-20 -FOA and the fluorine-free organic compound and of the concentrated sulfuric acid, which are supplied to the static mixer 10, assuming that all the water is present in the concentrated sulfuric acid phase in the liquid-liquid separation column 20.
  • the extraction treatment of the fluorine-free organic compound may be carried out continuously by using a contact type column so that the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, and the concentrated sulfuric acid are supplied so as to flow countercurrently.
  • the extraction of the fluorine-free organic compound may be carried out using a differential contact type extraction apparatus, which is a so-called “extraction column(tower)" (for example, a Karr column type extraction tower), by supplying one as a light liquid (i.e., lower density) and the other as a heavy liquid (i.e., higher density) from the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, and the concentrated sulfuric acid, and contacting the two liquids in countercurrent.
  • extraction column(tower) for example, a Karr column type extraction tower
  • a Karr column 30 One of the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, and the concentrated sulfuric acid is supplied as a heavy liquid to the upper portion of a cylindrical part 31 of the Karr column 30 and the other of those is supplied as a light liquid to the lower portion of the cylindrical part 31 (from a supply port 32) of the Karr column 30.
  • the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, and the concentrated sulfuric acid are stirred and mixed by passing counter-currently through the cylindrical part 31 in which a stirring disk (not shown) is installed, thereby the extraction of the fluorine-free organic compound can occur continuously in the Karr column 30, particularly in an extraction zone 35.
  • mixed liquid forms the C 2-20 -FOA phase and the concentrated sulfuric acid phase, and for example, liquid droplets of the C 2-20 -FOA phase can be dispersed as a dispersed phase in the concentrated sulfuric acid phase as a continuous phase, and vice versa.
  • the C 2-20 -FOA phase and the concentrated sulfuric acid phase are caused by phase separation, the light liquid is collected from a tank part 33 connected to an upper end 37 of a cylindrical part, and the heavy liquid is collected from a tank part 34 connected to a lower end 36 of a cylindrical part.
  • the correspondence relationship of the C 2-20 -FOA phase and the concentrated sulfuric acid phase with the heavy liquid and the light liquid is determined depending on the densities (or the specific gravities) of the C 2-20 -FOA phase and the concentrated sulfuric acid phase, and may vary depending on the type of the C 2-20 -FOA.
  • the amount of water present in the concentrated sulfuric acid phase is, in the case where the C 2-20 -FOA phase is the light liquid, the amount of water present in the concentrated sulfuric acid phase (heavy liquid) taken out from the outlet of the tank part 34, and thus it can be measured by directly analyzing the concentrated sulfuric acid phase sampled from the outlet of the tank part 34.
  • the C 2-20 -FOA phase is the heavy liquid, the amount of water present in the concentrated sulfuric acid phase (light liquid) taken out from the outlet of the tank part 33, and thus it can be measured by directly analyzing the concentrated sulfuric acid phase sampled from the outlet of the tank part 33.
  • the extraction treatment of the fluorine-free organic compound is carried out.
  • C 2-20 -FOA phase is characterized in that, since the fluorine-free organic compound is at least partially removed compared to the original mixture (the mixture containing the C 2-20 -FOA and the fluorine-free organic compound), the content ratio of the fluorine-free organic compound is reduced and the purity of the C 2-20 -FOA is improved. Therefore, the present method for purifying a C 2-20 -FOA can be understood as a method for treating the mixture containing the C 2-20 -FOA and the fluorine-free organic compound so as to at least partially remove the fluorine-free organic compound.
  • this extraction treatment of the fluorine-free organic compound can be carried out by contacting the mixture containing the C 2-20 -FOA and the fluorine-free organic compound with the concentrated sulfuric acid and then causing phase separation, this can be carried out conveniently compared to the conventional operation such as distillation which is carried out as a method for purifying a C 2-20 -FOA.
  • the C 2-20 -FOA phase obtained in the present method may be further subjected to distillation. In this case, since the fluorine-free organic compound has reduced, it is possible to reduce the load on distillation.
  • the concentrated sulfuric acid phase generated in the extraction treatment of the fluorine-free organic compound may be collected separately and used for any suitable use.
  • the concentrated sulfuric acid phase which is collected as such, may be recycled to the washing step with the sulfuric acid aqueous solution in the above dehydration treatment (for example in the next batch or in continuous manner).
  • the concentrated sulfuric acid and/or the sulfuric acid used and collected in the latter step may be recycled to the preceding step, whereby, since the amount of the concentrated sulfuric acid and/or the sulfuric acid to be used can be reduced while efficiently extracting (reducing or removing) the fluorine-free organic compound, the reduction of cost can be achieved.
  • the C 2-20 -FOA obtained in the form of the C 2-20 -FOA phase in the present method if necessary after being subjected to post-treatment, can be used as an emulsifier when producing polymer by emulsion polymerization.
  • the present method be understood as a method for producing or purifying an emulsifier containing the C 2-20 -FOA as a main component.
  • the present method when a reaction mixture after using the C 2-20 -FOA for emulsion polymerization is used as the mixture containing the C 2-20 -FOA and the fluorine-free organic compound, the present method can be understood as a method for regenerating the C 2-20 -FOA (or an emulsifier containing the C 2-20 -FOA as a main component).
  • the main component of the emulsifier refers to a component functioning as an emulsifier, which means a component occupying ⁇ 50 mass%, for example, ⁇ 70 mass%, particularly ⁇ 90 mass%, of the emulsifier.
  • a composition comprising a C 2-20 -FOA and a fluorine-free organic compound, wherein a content ratio of the fluorine-free organic compound in the composition is 0.001-0.1 mass-ppm.
  • the C 2-20 -FOA and the fluorine-containing organic compound can be the same as described above.
  • the content ratio of water in this composition may be, for example, ⁇ 0.1 mass%, and particularly ⁇ 0.05 mass%.
  • the remainder of the composition can be substantially composed of the C 2-20 -FOA and the purity of the C 2-20 -FOA can be the upper limit of measurement accuracy, for example, ⁇ 99.9 mass%.
  • the concentration of paraffin as the fluorine-free organic compound was measured as 7.2 mass-ppm, and the concentration of water was 200 mass-ppm, and the concentration of sulfuric acid was 1200 mass-ppm.
  • the concentration of succinic acid as the fluorine-free organic compound was measured as 4.3 mass-ppm, and the concentration of water was 200 mass-ppm, and the concentration of sulfuric acid was 1200 mass-ppm.
  • the concentration of oxalic acid as the fluorine-free organic compound was measured as 2.8 mass-ppm, and the concentration of water was 200 mass-ppm, and the concentration of sulfuric acid was 1200 mass-ppm.
  • the concentration of citric acid as the fluorine-free organic compound was measured as 9.8 mass-ppm, and the concentration of water was 200 mass-ppm, and the concentration of sulfuric acid was mass-1200 ppm.
  • the concentration of paraffin as the fluorine-free organic compound was measured as 5.5 mass-ppm, and the concentration of water was 450 mass-ppm, and the concentration of sulfuric acid was 4000 mass-ppm.
  • the concentration of paraffin as the fluorine-free organic compound was measured as 6.3 mass-ppm, and the concentration of water was 900 mass-ppm, and the concentration of sulfuric acid was 3200 mass-ppm.
  • the concentration of paraffin as the fluorine-free organic compound was measured as 11.2 mass-ppm, and the concentration of water was 250 mass-ppm, and the concentration of sulfuric acid was 1600 mass-ppm.
  • the present method for purifying a C 2-20 -FOAcan be suitably used as a method for producing a C 2-20 -FOA, in particular fluorocarboxylic acid, in which the fluorine-free organic compound is reduced.

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Description

    Technical Field
  • The present invention, which is defined in the claims, relates to a method for producing a fluorine-containing C2-20-organic acid (also abbreviated as "C2-20-FOA" hereinafter) .
    • Background Art
  • Conventionally, a C2-20-FOA is known and this fluorine-containing organic acid, in particular a C2-8-FOA, is used as an emulsifier, for example, for producing polymers by emulsion polymerization. In an emulsifier, impurities such as water and others may be mixed depending on a production method and/or a manner of use of an emulsifier. In order not to have unintended effect on emulsion polymerization, it is preferable that an amount of impurities in an emulsifier is small. In addition, emulsifiers are relatively expensive, so it is desirable to collect them after use and reuse them.
  • For example, JP-A-2010-65034 discloses that a mixture containing a fluorocarboxylic acid, which is one of emulsifiers, and water is dehydrated by contacting it with a concentrated sulfuric acid to obtain a dehydrated fluorocarboxylic acid solution, and then the dehydrated fluorocarboxylic acid solution is purified by distillation operation.
  • EP-A-2 321 248 ( WO 2010/027103 ) discloses a process for preparing a fluorocarboxylic acid, comprising the steps of (i) removing from a mixture containing a fluorocarboxylic acid and water at least a part of said water to obtain a dehydrated fluorocarboxylic acid solution and (ii) purifying said dehydrated fluorocarboxylic acid solution by common means, such as distillation or crystallization.
  • Furthermore, EP-A-0 566 974 ( US 5,312,935 ) describes a process for the purification of an impure perfluorinated carboxylic acid, comprising oxidizing the impurities in a reaction mixture comprising < 9 wt.% of water, impure perfluorinated carboxylic acid and an oxidant, thereby purifying the acid, and isolating the resulting purified perfluorinated carboxylic acid.
    • Summary of Invention Technical Problem
  • The present inventors have been focused on that, in some cases, a fluorine-free (or fluorine-non-containing) organic compound is mixed as an impurity in a C2-20-FOA. Such a fluorine-free organic compound includes, for example, fluorine-free carboxylic acids, hydrocarbons and polyethers which can be used as dispersion stabilizers (stabilizing aids) in emulsion polymerization or for other purposes.
  • Since such a fluorine-free organic compound is usually present as a trace component in a C2-20-FOA, it is difficult to separate by distillation operation. If a fluorine-free organic compound can be effectively removed from a C2-20-FOA, it is convenient, for example, because it can regenerate the spent C2-20-FOA as an emulsifier and reuse it as an emulsifier.
  • An object of the present invention is to provide a method which is possible to effectively remove a fluorine-free organic compound from a mixture containing a C2-20-FOA and a fluorine-free organic compound, in other words, to provide a method for producing a C2-20-FOA with reduced fluorine-free organic compound. A further object of the present invention is to provide a novel composition, which can be obtained by such a method, comprising a C2-20-FOA.
    • Solution to Problem
  • Conventionally, in post-treatment or regeneration treatment of the fluorocarboxylic acid which is one of emulsifiers, a concentrated sulfuric acid has been used for dehydrating from a mixture containing fluorocarboxylic acid and water (see JP-A-2010-65034 ). After contacting and mixing a mixture containing fluorocarboxylic acid and water with a concentrated sulfuric acid, it has been separated into an organic phase and an aqueous phase to obtain fluorocarboxylic acid in the form of the organic phase. If it is assumed that an organic compound is mixed as an impurity in such a contacting and mixing system containing fluorocarboxylic acid, water and a concentrated sulfuric acid, it is generally considered that the organic compound is distributed to the organic phase rather than the aqueous phase.
  • However, the present inventors have obtained unique knowledge that a fluorine-free organic compound can be extracted from a C2-20-FOA phase into a concentrated sulfuric acid phase (or at least partially removed from a C2-20-FOA) by contacting a mixture containing a C2-20-FOA and a fluorine-free organic compound with a concentrated sulfuric acid in a state in which substantially no water or a very small amount of water is present. As a result of further intensive studies, the present inventors have completed the present invention.
  • Thus, the present invention provides a method for purifying a fluorine-containing C2-20-organic acid (A), comprising
    • contacting a mixture containing an acid (A) and a fluorine-free organic compound (B) with concentrated sulfuric acid and then
    • separating an acid (A) phase from a concentrated sulfuric acid phase,
    wherein
    • the acid (A) is selected from C2-20-fluorocarboxylic acids, C2-20-fluorosulfonic acids, and salts thereof,
    • the contacting is conducted such that an amount of water present in the concentrated sulfuric acid phase is ≤ 10 mass-%, and
    • the acid (A) is obtained in form of the acid (A) phase having a reduced content ratio of the compound (B) compared with the mixture.
  • Preferred embodiments of the present invention are as defined in the appended dependent claims and/or in the following detailed description.
    • Advantageous Effects of Invention
  • According to the present invention, in the case of contacting a mixture containing a C2-20-FOA and a fluorine-free organic compound with a concentrated sulfuric acid and then separating a C2-20-FOA phase from a concentrated sulfuric acid phase, this contacting is conducted such that an amount of water present in the concentrated sulfuric acid phase is ≤ 10 mass% and thus the C2-20-FOA can be obtained in the form of the C2-20-FOA phase having a reduced content ratio of a fluorine-free organic compound compared with said mixture. Thereby, there is provided a method for producing a C2-20-FOA with reduced fluorine-free organic compound.
    • Brief Description of Drawings
    • Fig. 1 (a) is a schematic sectional view showing a configuration of a static mixer, and Fig. 1 (b) is a schematic view showing a configuration of a liquid-liquid separation column.
    • Fig. 2 is a schematic sectional view showing a configuration of a Karr column.
    Description of Embodiments
  • The present method for purifying a C2-20-FOA will be described in detail below through embodiments of the present invention.
  • First, a mixture containing a C2-20-FOA and a fluorine-free organic compound is prepared.
  • The C2-20-FOA is selected from fluorine-containing C2-20-carboxylic acids (C2-20-fluorocarboxylic acids) and salts thereof, and fluorine-containing C2-20-sulfonic acids (C2-20-fluorosulfonic acids) and salts thereof.
  • Examples of the C2-20-fluorocarboxylic acid include the compounds of formula (i):

            X-Rf-COOH     (i)

    wherein X is H, F or Cl, Rf is linear or branched C1-19-fluoroalkylene, a C1-19-group having a monooxyfluoroalkylene group or a C1-19-group having a polyoxyfluoroalkylene group.
  • The linear or branched C1-19-fluoroalkylene group in the above-mentioned Rf group may be CaFbH2a-b (wherein a is an integer of 1-19 and b is an integer of ≤ 2a). Examples of such a group include CF2, C2F4, C3F6, C4F8, C5F10, C6F12, C7F14, CHF, C2F3H, C2F2H2, C2FH3, C3F5H, C3F4H2, C3F3H3, C3F2H4, C3F1H5, C4F7H, C4F6H2, C4F5H3, C4F4H4, C4F3H5, C4F2H6, C4FH7, C5F9H, C5F8H2, C5F7H3, C5F6H4, C5F5H5, C5F4H6, C5F3H7, C5F2H8, C5FH9, C6F11H, C6F10H2, C6F9H3, C6F8H4, C6F7H5, C6F6H6, C6F5H7, C6F4H8, C6F3H9, C6F2H10, C6FH11, C7F13H, C7F12H2, C7F11H3, C7F10H4, C7F9H5, C7F8H6, C7F7H7, C7F6H8, C7F5H9, C7F4H10, C7F3H11, C7F2H12 and C7FH13.
  • Examples of the C1-19-group having a mono- or polyoxyfluoroalkylene group in the above-mentioned Rf group include the groups of the formulae:

            (CF2)l-(CF2OCF2)m-(CF2OCF(CF3))n     formula (a)

            (CF2)l-(CHFOCF2)m-(CF2OCF(CF3))n     formula (b)

            (CF2)l-(CF2OCHF)m-(CF2OCF(CF3))n     formula (c)

            (CHF)l-(CF2OCF2)m-(CF2OCF(CF3))n     formula (d)

            (CHF)l-(CHFOCF2)m-(CF2OCF(CF3))n     formula (e)

            (CHF)l-(CF2OCHF)m-(CF2OCF(CF3))n     formula (f)

    wherein l is 0 or an integer of 1-17, m is 0 or an integer of 1-9 and n is an integer of 0-6, provided that l + 2m + 3n does not exceed 19 and that a case where m and n are 0 is excluded.
  • Further, in the above formulae, the order of presence of the respective repeating units in parentheses is arbitrary.
  • In formula (i), more preferably, X is H or F, Rf is a C1-19-group having a mono- or polyoxyfluoroalkylene group, further preferably Rf is a C1-7-group, particularly a C1-6-group, each having a mono- or polyoxyfluoroalkylene group.
  • Further preferably, the C2-20-fluorocarboxylic acid is a perfluorocarboxylic acid of the formula (i-a):

            X-Rf-COOH     (i-a)

    • wherein X is H or F, Rf is a group of the formula (a)

              (CF2)l-(CF2OCF2)m-(CF2OCF(CF3))n     formula (a)

    • wherein, in the above formula (a), l is 0 or an integer of 1-17, m is 0 or an integer of 1-9 and n is an integer of 0-6, provided that (l+2m+3n) does not exceed 19, that a case where m and n are 0 is excluded and that the order of presence of the respective repeating units in parentheses is arbitrary.
  • In the above-mentioned fluorocarboxylic acid, the number of carbon atoms is preferably 4-10, more preferably 5-8, and particularly preferably 6-8.
  • Examples of the C5-8-fluorocarboxylic acid as a preferred embodiment include

            CF3OCF(CF3)CF2OCF(CF3)COOH,

            CF3CF2OCF2CF2OCF2COOH,

            CF3OCF2CF2CF2OCHFCF2COOH,

            CF3CF2OCF2CF2OCF2COOH,

            CF3OCF2CF2CF2OCHFCF2COOH,

            CF3(CF2)4COOH,

            CF3CF2CF2OCF(CF3)COOH,

            H(CF2)6COOH,

            H(CF2)4COOH,

            CH2=CFCF2OCF(CF3)COOH,

            CF3(CF2)6COOH,

    and

            CF3CF2CF2OCF2CF2OCF(CF3)COOH.

  • Examples of the C2-20-fluorosulfonic acid include perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluorohexanesulfonic acid, CF2=CFOCF2CF2SO3H, CF2=CFOCF2CF(CF3)OCF2CF2SO3H and CF3(CF2)8SO3H.
  • Examples of the salts of the fluorocarboxylic acid and the fluorosulfonic acid include a salt having a monovalent cation as a counter ion, for example, alkali metal salts such as potassium salts and sodium salts, ammonium salts and amine salts (for example, alkylamine salts such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine).
  • The fluorine-free organic compound may be an organic compound containing no fluorine. Examples of the fluorine-free organic compound include a fluorine-free C1-50-organic compound. Examples of the C1-50-organic compound include at least one of a fluorine-free C1-50-carboxylic acid and derivatives thereof, a fluorine-free C8-50-hydrocarbon, a fluorine-free C6-50-phenol, a fluorine-free C1-30-alcohol, a fluorine-free C8-50-polyether and a fluorine-free C10-20-alkyl group-containing ionic compound. The number of carbon atoms of the above organic compounds is preferably 10-40, more preferably 14-35.
  • The fluorine-free C1-50-carboxylic acid may have one or more carboxyl groups. Examples of the derivative of the fluorine-free C1-50-carboxylic acid include a carboxylic acid ester and/or those having substituents such as hydroxy and alkoxy. Examples of the fluorine-free C1-50-carboxylic acid and derivatives thereof include the followings:
    • a fluorine-free aromatic C8-50-carboxylic acid and esters thereof, for example, phthalic acid, phthalic acid anhydride, phthalimide, phthalate (for example, sodium salt or potassium salt), phthalic acid mono- or di- alkyl ester (for example, dimethyl phthalate, diethyl phthalate, diallyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinormal hexyl phthalate, bis (2-ethylhexyl) phthalate, dinormal octyl phthalate, diisononyl phthalate, dinonyl phthalate, diisodecyl phthalate and bisbutyl benzyl phthalate), benzoic acid, benzoic acid alkyl ester (for example, methyl benzoate, ethyl benzoate, propyl benzoate and butyl benzoate), salicylic acid, salicylic acid alkyl ester (for example, methyl salicylate, ethyl salicylate, propyl salicylate and butyl salicylate), gallic acid, gallic acid alkyl ester (for example, methyl gallate, ethyl gallate, propyl gallate and butyl gallate), melitic acid, melitic acid anhydride, cinnamic acid, cinnamic acid anhydride, cinnamic acid alkyl ester (for example, methyl cinnamate, ethyl cinnamate, propyl cinnamate and butyl cinnamate);
    • a fluorine-free aliphatic C1-50-carboxylic acid and esters thereof, for example, formic acid, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, CF3(CF2)6COOH, CF3(CF2)8COOH, H(CF2)8COOH, H(CF2)10COOH, CF3CF2CF2OCF(CF3)CF2OCF(CF3)COOH, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and 1,2,3-propanetricarboxylic acid, and alkyl esters thereof (for example, methyl ester, ethyl ester, propyl ester and butyl ester), and/or those in which one or more hydrogen atoms are substituted by e.g. hydroxy or alkoxy (for example, citric acid).
  • The number of carbon atoms of the carboxylic acid and its derivative is preferably 1-30, more preferably 1-20.
  • Examples of the fluorine-free C8-50-hydrocarbon include a linear, branched or alicyclic and saturated or unsaturated C8-50-hydrocarbon. The number of carbon atoms is more preferably 10-40, even more preferably 20-40. A saturated C20-40-hydrocarbon is sometimes referred to as paraffin. Since paraffin generally has a molecular weight distribution and has a wide range of boiling points, it is extremely difficult to separate paraffin by distillation operation.
  • The fluorine-free C6-50-phenol may be a monovalent or polyvalent phenol compound. Examples of the fluorine-free C6-50-phenols include phenol, di-t-butylphenol, cresol, naphthol, hydroquinone, catechol, resorcinol, pyrogallol, phloroglucinol and hexahydroxybenzene.
  • The fluorine-free C1-30-alcohol may be a monovalent or polyvalent alcohol compound. Examples of the fluorine-free C1-30-alcohol include methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexane-1-ol, heptan-1-ol, octan-1-ol, nonan-1-ol, decane-1-ol, undecan-1-ol, dodecan-1-ol, tridecan-1-ol, tetradecan-1-ol, pentadecan-1-ol, hexadecan-1-ol, heptadecan-1-ol, octadecan-1-ol, nonadecan-1-ol, icosan-1-ol, heneicosan-1-ol, docosan-1-ol, tricosan-1-ol, tetracosan-1-ol, pentacosan-1-ol, hexacosan-1-ol, heptacosan-1-ol, octacosan-1-ol, nonacosan-1-ol, triacontan-1-ol, policosanol, 2-methylpropan-1-ol, 3-methylbutan-1-ol, propan-2-ol, butan-2-ol, pentan-2-ol, hexane-2-ol, heptan-2-ol, 2-methylbutan-1-ol, cyclohexanol, 2-methylpropan-2-ol, 2-methylbutan-2-ol, 2-methylpentan-2-ol, 2-methylhexan-2-ol, 2-methylheptan-2-ol, 3-methylpentan-3-ol, 3-methyloctan-3-ol, ethylene glycol, glycerin, hydroquinone, catechol and 4-t-butyl catechol.
  • Examples of the fluorine-free C8-50-polyether include the followings:
    • a C8-50-polyethylene glycol, a C8-50-polypropylene glycol, a C8-50-polyethylene/polypropylene glycol (herein, "polyethylene/polypropylene" means a group composed of an ethylene portion and a propylene portion), particularly a C8-50-polyether polyol such as C8-50-polyethylene glycol-polypropylene glycol-block ether;
    • a C8-50-poly (oxyalkylene) alkyl ether such as a C8-50-poly (oxyethylene) monoalkyl ether, a C8-50-poly (oxyethylene) dialkyl ether, a C8-50-poly (oxypropylene) monoalkyl ether, a C8-50-poly (oxypropylene) dialkyl ether, a C8-50-poly (oxyethylene) / (oxypropylene) monoalkyl ether, a C8-50-poly(oxyethylene)/(oxypropylene) dialkyl ether (in the above, "(oxyethylene)/(oxypropylene)" means a group composed of an oxyethylene portion and an oxypropylene portion);
    • a C8-50-poly (oxyalkylene) arylalkyl ether such as a C8-50-poly (oxyethylene) monoaryl alkyl ether, a C8-50-poly (oxyethylene) diaryl alkyl ether, a C8-50-poly (oxypropylene) monoaryl alkyl ether, a C8-50-poly (oxypropylene) diaryl alkyl ether, a C8-50-poly (oxyethylene) / (oxypropylene) monoaryl alkyl ether, a C8-50-poly (oxyethylene) / (oxypropylene) diarylalkyl ether (in the above, "(oxyethylene)/(oxypropylene)" means a group composed of an oxyethylene portion and an oxypropylene portion).
  • Examples of the fluorine-free C10-20-alkyl group-containing ionic compound include the followings:
    • a C10-20-alkyl sulfonate, for example, dodecyl sulfate;
    • a C10-20-alkylamine salt, for example, dodecylamine hydrochloride;
    • a C10-20-alkyl quaternary ammonium salt, for example, hexadecyl trimethyl ammonium bromide;
    • a C10-20-alkyl betaine, for example, dodecyl betaine;
    • a C10-20-alkylamine oxide salt, for example, dodecyldimethylamine oxide.
  • However, the fluorine-free organic compound is not limited thereto, and it may be any other appropriate fluorine-free organic compound which can be added (and/or can be mixed), for example, as a dispersion stabilizer (a stabilizing aid), a surfactant, a chelating agent, a plasticizer, an initiator, a polymerization inhibitor, a chain transfer agent, an adhesion preventing agent and a machine oil.
  • The content ratio of the fluorine-free organic compound in the mixture containing the C2-20-FOA and the fluorine-free organic compound may be, for example, ≤ 1000 mass-ppm, particularly ≤ 500 mass-ppm, ≤ 200 mass-ppm, ≤ 100 mass-ppm, ≤ 50 mass-p, ≤ 30 mass-ppm, ≤ 20 mass-ppm, ≤ 10 mass-ppm, and but not particularly limited, it may be, for example, in the range of > 0.1 mass-ppm. The content ratio of the fluorine-free organic compound in the above-mentioned mixture may be, for example, > 0.1 to 100 mass-ppm, particularly 0.2-500 mass-ppm, 0.5-200 mass-ppm, 0.5-100 mass-ppm, 1-50 mass-ppm, 1-30 mass-ppm, 1-20 mass-ppm, 1-10 mass-ppm.
  • The mixture containing the C2-20-FOA and the fluorine-free organic compound may contain other component which is, for example, a concentrated sulfuric acid, water, an inorganic substance (for example, an inorganic acids, a metal, other inorganic compound or elemental substance) and divalent metal salt. However, the content of water in the mixture containing the C2-20-FOA and the fluorine-free organic compound is appropriately selected, according to the specific operation of the contact, so as to satisfy the condition relating to the amount of water in the contacting described later.
  • The mixture containing the C2-20-FOA and the fluorine-free organic compound can be obtained by any suitable method, and, for example, it may be those derived from a reaction mixture after synthesizing the C2-20-FOA or those derived from a reaction mixture after using the C2-20-FOA for emulsion polymerization. Although not limiting to the present invention, for example, the mixture containing the C2-20-fluorocarboxylic acid and the fluorine-free organic compound includes a reaction mixture obtained by a reaction (synthesis reaction) which produces the corresponding fluorocarboxylic acid by hydrolyzing the C2-20-fluorocarboxylic acid fluoride, and a reaction mixture obtained by a reaction (regeneration reaction) which produces the corresponding fluorocarboxylic acid by acidifying the C2-20-fluorocarboxylic acid salt used in the emulsion polymerization. In the present specification, the term "derived" means that it may be obtained by appropriately subjecting the reaction mixture to post-treatment such as filtration, washing, deionization, dehydration and purification.
  • The mixture containing the C2-20-FOA and the fluorine-free organic compound may be previously subjected to dehydration treatment. By the dehydration treatment, the amount of water in the mixture can be reduced to a desired level (for example, to a substantially negligible level) so that it is possible to easily attain the condition relating to the amount of water in the contacting described later. The dehydration treatment may be carried out in either a batch manner or a continuous manner.
  • In one embodiment of the present invention, the dehydration treatment can be carried out by washing a mixture containing a precursor of the above-mentioned "the mixture containing the C2-20-FOA and the fluorine-free organic compound" as well as water with a sulfuric acid aqueous solution having a sulfuric acid concentration of ≥ 70 mass%. The dehydration treatment can be carried out by, for example, contacting a mixture containing the C2-20-FOA, the fluorine-free organic compound and water with a sulfuric acid aqueous solution having a sulfuric acid concentration of ≥ 70 mass%, for example ≥ 80 mass%, particularly ≥ 90 mass%, more particularly ≥ 96 mass%, further particularly ≥ 98 mass%, more further particularly ≤ 99.9 mass%, or typically a concentrated sulfuric acid, and then causing phase separation into a C2-20-FOA phase (or an organic phase or a fluorous phase) and a sulfuric acid phase (it can be understood as an aqueous phase since water is more distributed to the sulfuric acid phase than the fluorine-containing organic acid phase) to obtain the above-mentioned "the mixture containing the C2-20-FOA and the fluorine-free organic compound" in the form of the C2-20-FOA phase. Herein, the sulfuric acid concentration means the sulfuric acid concentration of the sulfuric acid phase (the aqueous phase) during the dehydration treatment. The amount ratio of the mixture containing the C2-20-FOA, the fluorine-free organic compound and water and the sulfuric acid aqueous solution is not particularly limited as long as the above sulfuric acid concentration can be maintained.
  • According to this embodiment, the mixture containing the C2-20-FOA, the fluorine-free organic compound as well as water is subjected to contacting with a sulfuric acid aqueous solution (particularly a concentrated sulfuric acid) for the purpose of dehydration, and then is subjected to contacting with a concentrated sulfuric acid for the purpose of extraction (reduction or removal) of the fluorine-free organic compound, which will be described later. Therefore in summary, it will be washed at least twice with a sulfuric acid (especially a concentrated sulfuric acid). The contacting with a sulfuric acid aqueous solution for the purpose of dehydration may be carried out twice or more until the desired dehydration (water content) level is reached. In this case, when it is summed with the contacting with a concentrated sulfuric acid for the purpose of extraction of the fluorine-free organic compound, schematically, it will be washed three or more times with sulfuric acid (especially concentrated sulfuric acid). The specific operation of the contacting with a sulfuric acid aqueous solution for the purpose of dehydration may be the same as the specific operation of the contacting with a concentrated sulfuric acid for the purpose of extraction (reduction or removal) of the fluorine-free organic compound, which is described later, except that what is phase separated from the C2-20-FOA phase is not a concentrated sulfuric acid phase but a sulfuric acid phase (an aqueous phase). It should be noted that, when the C2-20-FOA is in the form of a salt of the acid compound, it is acidified by contacting with a sulfuric acid or concentrated sulfuric acid to produce the corresponding acid compound.
  • However, the dehydration treatment is not limited to washing with a sulfuric acid, but any other appropriate method, for example, which is carried out by contacting the mixture containing the C2-20-FOA, the fluorine-free organic compound and water with a water-absorbing substance such as diphosphorus pentaoxide or zeolite (in the presence or absence of the above-mentioned sulfuric acid aqueous solution). Examples of zeolite include aluminosilicate.
  • The water content of the mixture containing the C2-20-FOA and the fluorine-free organic compound, which has been previously subjected to dehydration treatment, is, for example, ≤ 1.0 mass%, preferably ≤ 0.7 mass%, particularly preferably ≤ 0.2 mass%.
  • Then, in the present method for purifying the C2-20-FOA, to extract (reduce or eliminate) the fluorine-free organic compound, the mixture containing the C2-20-FOA and the fluorine-free organic compound, as described above, is contacted with a concentrated sulfuric acid (hereinafter referred to as "extraction treatment of the fluorine-free organic compound").
  • In the present invention, "(a) concentrated sulfuric acid" refers to a sulfuric acid aqueous solution having a sulfuric acid concentration of ≥ 90 mass%. The sulfuric acid concentration of the concentrated sulfuric acid is, for example, ≥ 92 mass%, particularly ≥ 96 mass%, typically ≥ 98 mass%.
  • The mass ratio (the flow ratio in the case of continuous manner) of the mixture containing the C2-20-FOA and the fluorine-free organic compound, and the concentrated sulfuric acid is not particularly limited as long as it can satisfy the condition relating to the amount of water in the contacting described later. However, it can be, for example, 10:1 to 1:1, in particular 10:2 to 10:5.
  • In the extraction treatment of the fluorine-free organic compound, it is preferable to stir and mix the mixture containing the C2-20-FOA and the fluorine-free organic compound and the concentrated sulfuric acid so as to contact sufficiently with each other. For example, it is preferable to disperse the C2-20-FOA phase in the concentrated sulfuric acid phase or to disperse the concentrated sulfuric acid phase in the C2-20-FOA phase. More specifically, for example, droplets of the C2-20-FOA phase can be dispersed as a dispersed phase in the concentrated sulfuric acid phase as a continuous phase. This promotes the contacting and the mass transfer between the concentrated sulfuric acid phase as the continuous phase and the C2-20-FOA phase as the dispersed phase and therefore the fluorine-free organic compound can be effectively extracted from the C2-20-FOA phase (or an organic phase or a fluorous phase) into the concentrated sulfuric acid phase. The dispersed phase and the continuous phase may be reversed. Thereafter, the mixture obtained by contacting them undergoes phase separation into the C2-20-FOA phase and the concentrated sulfuric acid phase. The C2-20-FOA and the concentrated sulfuric acid have low solubility with respect to each other and naturally phase-separate by substantially removing the stirring and mixing force. Then, the targeted C2-20-FOA phase is separated and collected from the concentrated sulfuric acid phase.
  • The contacting of the mixture containing the C2-20-FOA and the fluorine-free organic compound with the concentrated sulfuric acid in the extraction treatment of the fluorine-free organic compound is conducted such that the amount of water present in the concentrated sulfuric acid phase is ≤ 10 mass%. Thus, by containing the mixture containing the C2-20-FOA and the fluorine-free organic compound with the concentrated sulfuric acid in a state in which substantially no water or a very small amount of water is present, the fluorine-free organic compound can be extracted from the C2-20-FOA phase into the concentrated sulfuric acid phase (or at least partially removed from the C2-20-FOA).
  • In the present invention, "the(an) amount of water present in the concentrated sulfuric acid phase" means the amount of water present in the concentrated sulfuric acid phase, before, during or after separating the C2-20-FOA phase. The amount of water may be determined by calculation if possible (for example, wherein the concentrated sulfuric acid phase is considered to be substantially uniform irrespective of its part) or may be measured by directly analyzing the concentrated sulfuric acid phase sampled from any appropriate part of the apparatus performing the separation operation. Since the amount of water present in the concentrated sulfuric acid phase can be considered to be substantially the same from the contact interface between the C2-20-FOA phase and the concentrated sulfuric acid phase to the outlet of the apparatus, the outlet concentration obtained by sampling the concentrated sulfuric acid phase withdrawn from the outlet of the apparatus and measuring its amount of water can be set as "the amount of water present in the concentrated sulfuric acid phase", without problems. The analysis can be carried out, for example, by Karl Fischer method. The amount of water may be ≤ 10 mass%, preferably ≤ 8 mass%, particularly ≤ 4 mass%, and more preferably ≤ 2 mass%.
  • As described above, the C2-20-FOA can be obtained in the form of the C2-20-FOA phase having the reduced content ratio of the fluorine-free organic compound as compared with the original mixture (mixture containing the C2-20-FOA and the fluorine-free organic compound). It should be noted that the fluorine-free organic compound does not need to be extracted into the concentrated sulfuric acid phase as it is, and the fluorine-free organic compound may be reduced or removed in the C2-20-FOA phase as compared with the original mixture. For example, the fluorine-free organic compound may be extracted in a state of being decomposed into the concentrated sulfuric acid phase.
  • The content ratio of the fluorine-free organic compound in the resulting C2-20-FOA phase is preferably, for example, ≤ 0.1 mass-ppm, and particularly preferably ≤ 0.05 mass-ppm. The remainder of the C2-20-FOA phase is preferably composed of the C2-20-FOA.
  • In the present invention, the extraction treatment of the fluorine-free organic compound may be carried out in either a batch manner or a continuous manner. In the case of carrying out in a batch manner, the mixture containing the C2-20-FOA and the fluorine-free organic compound is thoroughly mixed with the concentrated sulfuric acid, and then the mixed solution is left to stand (for example, mixing is stopped after mixing for a predetermined time) to phase-separate into the targeted C2-20-FOA phase containing the C2-20-FOA and the concentrated sulfuric acid phase and collect the C2-20-FOA phase. If necessary, the resultant C2-20-FOA phase can be again mixed with a concentrated sulfuric acid, and then the mixture can be left to stand to obtain the C2-20-FOA phase having a smaller amount of the fluorine-free organic compound. This operation may be repeated until the concentration of the fluorine-free organic compound in the C2-20-FOA phase becomes lower than the desired level.
  • Furthermore, the extraction treatment of the fluorine-free organic compound may include a step of continuously contacting a C2-20-FOA phase and the concentrated sulfuric acid phase in a liquid-liquid heterophasic dispersion system consisting of the C2-20-FOA phase and the concentrated sulfuric acid phase and a step of phase-separating the C2-20-FOA phase and the concentrated sulfuric acid phase.
  • For example, referring to Fig. 1 (a) and (b), it can be carried out as follows using a static mixer 10 and a liquid-liquid separation column 20. The mixture containing the C2-20-FOA and the fluorine-free organic compound, and the concentrated sulfuric acid are supplied from any one and the other of supply ports 11 and 12 to the static mixer 10, respectively. The mixture containing the C2-20-FOA and the fluorine-free organic compound, and the concentrated sulfuric acid are stirred and mixed by passing through the static mixer 10 in which an element 13 is installed, and the extraction of the fluorine-free organic compound can occur continuously in the static mixer 10. Thus mixed solution is discharged from a discharge port 14, and then supplied to the liquid-liquid separation column 20. The mixed solution supplied from the supply port 23 is liquid-liquid separated into a heavy liquid 21 and a light liquid 22 in the liquid-liquid separation column 20, and therefore the C2-20-FOA phase can be collected. The correspondence relationship of the C2-20-FOA phase and the concentrated sulfuric acid phase with the heavy liquid and the light liquid is determined depending on the densities (or the specific gravities) of the C2-20-FOA phase and the concentrated sulfuric acid phase, and may vary depending on the type of the C2-20-FOA. In such an embodiment, "the amount of water present in the concentrated sulfuric acid phase" is the amount of water present in the concentrated sulfuric acid phase withdrawn from the outlet of the liquid-liquid separation column 20. It may be measured by directly analyzing the concentrated sulfuric acid phase sampled from the outlet of the apparatus, or may be calculated from respective moisture contents of the mixture containing the C2-20-FOA and the fluorine-free organic compound and of the concentrated sulfuric acid, which are supplied to the static mixer 10, assuming that all the water is present in the concentrated sulfuric acid phase in the liquid-liquid separation column 20.
  • Alternatively, the extraction treatment of the fluorine-free organic compound may be carried out continuously by using a contact type column so that the mixture containing the C2-20-FOA and the fluorine-free organic compound, and the concentrated sulfuric acid are supplied so as to flow countercurrently. More specifically, the extraction of the fluorine-free organic compound may be carried out using a differential contact type extraction apparatus, which is a so-called "extraction column(tower)" (for example, a Karr column type extraction tower), by supplying one as a light liquid (i.e., lower density) and the other as a heavy liquid (i.e., higher density) from the mixture containing the C2-20-FOA and the fluorine-free organic compound, and the concentrated sulfuric acid, and contacting the two liquids in countercurrent.
  • For example, referring to Fig. 2, it can be carried out as follows using a Karr column 30. One of the mixture containing the C2-20-FOA and the fluorine-free organic compound, and the concentrated sulfuric acid is supplied as a heavy liquid to the upper portion of a cylindrical part 31 of the Karr column 30 and the other of those is supplied as a light liquid to the lower portion of the cylindrical part 31 (from a supply port 32) of the Karr column 30. The mixture containing the C2-20-FOA and the fluorine-free organic compound, and the concentrated sulfuric acid are stirred and mixed by passing counter-currently through the cylindrical part 31 in which a stirring disk (not shown) is installed, thereby the extraction of the fluorine-free organic compound can occur continuously in the Karr column 30, particularly in an extraction zone 35. Thus mixed liquid forms the C2-20-FOA phase and the concentrated sulfuric acid phase, and for example, liquid droplets of the C2-20-FOA phase can be dispersed as a dispersed phase in the concentrated sulfuric acid phase as a continuous phase, and vice versa. The C2-20-FOA phase and the concentrated sulfuric acid phase are caused by phase separation, the light liquid is collected from a tank part 33 connected to an upper end 37 of a cylindrical part, and the heavy liquid is collected from a tank part 34 connected to a lower end 36 of a cylindrical part. The correspondence relationship of the C2-20-FOA phase and the concentrated sulfuric acid phase with the heavy liquid and the light liquid is determined depending on the densities (or the specific gravities) of the C2-20-FOA phase and the concentrated sulfuric acid phase, and may vary depending on the type of the C2-20-FOA. In such an embodiment, "the amount of water present in the concentrated sulfuric acid phase" is, in the case where the C2-20-FOA phase is the light liquid, the amount of water present in the concentrated sulfuric acid phase (heavy liquid) taken out from the outlet of the tank part 34, and thus it can be measured by directly analyzing the concentrated sulfuric acid phase sampled from the outlet of the tank part 34. On the other hand, it is, in the case where the C2-20-FOA phase is the heavy liquid, the amount of water present in the concentrated sulfuric acid phase (light liquid) taken out from the outlet of the tank part 33, and thus it can be measured by directly analyzing the concentrated sulfuric acid phase sampled from the outlet of the tank part 33.
  • As described above, the extraction treatment of the fluorine-free organic compound is carried out. Thus obtained C2-20-FOA phase is characterized in that, since the fluorine-free organic compound is at least partially removed compared to the original mixture (the mixture containing the C2-20-FOA and the fluorine-free organic compound), the content ratio of the fluorine-free organic compound is reduced and the purity of the C2-20-FOA is improved. Therefore, the present method for purifying a C2-20-FOA can be understood as a method for treating the mixture containing the C2-20-FOA and the fluorine-free organic compound so as to at least partially remove the fluorine-free organic compound.
  • Since this extraction treatment of the fluorine-free organic compound can be carried out by contacting the mixture containing the C2-20-FOA and the fluorine-free organic compound with the concentrated sulfuric acid and then causing phase separation, this can be carried out conveniently compared to the conventional operation such as distillation which is carried out as a method for purifying a C2-20-FOA. In addition, the C2-20-FOA phase obtained in the present method may be further subjected to distillation. In this case, since the fluorine-free organic compound has reduced, it is possible to reduce the load on distillation.
  • On the other hand, the concentrated sulfuric acid phase generated in the extraction treatment of the fluorine-free organic compound may be collected separately and used for any suitable use. For example, the concentrated sulfuric acid phase, which is collected as such, may be recycled to the washing step with the sulfuric acid aqueous solution in the above dehydration treatment (for example in the next batch or in continuous manner). When the dehydration treatment and/or the extraction treatment is carried out twice or more, the concentrated sulfuric acid and/or the sulfuric acid used and collected in the latter step may be recycled to the preceding step, whereby, since the amount of the concentrated sulfuric acid and/or the sulfuric acid to be used can be reduced while efficiently extracting (reducing or removing) the fluorine-free organic compound, the reduction of cost can be achieved.
  • Although not intended to limit the present invention, the C2-20-FOA obtained in the form of the C2-20-FOA phase in the present method, if necessary after being subjected to post-treatment, can be used as an emulsifier when producing polymer by emulsion polymerization. In this case, since the fluorine-free organic compound is reduced and the purity of the C2-20-FOA is improved, polymerization rate can be increased. Therefore, the present method be understood as a method for producing or purifying an emulsifier containing the C2-20-FOA as a main component. In the present invention, when a reaction mixture after using the C2-20-FOA for emulsion polymerization is used as the mixture containing the C2-20-FOA and the fluorine-free organic compound, the present method can be understood as a method for regenerating the C2-20-FOA (or an emulsifier containing the C2-20-FOA as a main component). The main component of the emulsifier refers to a component functioning as an emulsifier, which means a component occupying ≥ 50 mass%, for example, ≥ 70 mass%, particularly ≥ 90 mass%, of the emulsifier.
  • It is desirable that the fluorine-free organic compound is completely removed in the C2-20-FOA phase obtained by the present method, but a composition containing the C2-20-FOA and the fluorine-free organic compound is acceptable.
  • According to the present method, it can be obtained a composition comprising a C2-20-FOA and a fluorine-free organic compound, wherein a content ratio of the fluorine-free organic compound in the composition is 0.001-0.1 mass-ppm. The C2-20-FOA and the fluorine-containing organic compound can be the same as described above. The content ratio of water in this composition may be, for example, ≤ 0.1 mass%, and particularly ≤ 0.05 mass%. The remainder of the composition can be substantially composed of the C2-20-FOA and the purity of the C2-20-FOA can be the upper limit of measurement accuracy, for example, ≥ 99.9 mass%.
    • Examples
  • Hereinafter, the present invention will be described with examples. The concentration measurements in the following Examples and Comparative Examples were as follows.
    • The concentration of paraffin among the fluorine-free organic compound in the fluorine-containing organic acid phase was measured by gas chromatographic analysis. The analysis conditions used for the gas chromatographic analysis were as follows.
      • Detector: FID
      • Sample injection amount: 1 µL
      • Split ratio: 1/20
    • The concentrations of carboxylic acid compounds (more specifically succinic acid, oxalic acid, citric acid) among the fluorine-free organic compound in the fluorine-containing organic acid phase were measured by HPLC analysis.
    • The concentration of water was measured by Karl Fischer method.
    • The sulfuric acid concentration was measured by ion chromatography analysis.
    Production Example 1
  • 50 g of concentrated sulfuric acid having a concentration of 90 mass% (water of 10 mass%) was added to 100 g of a solution containing paraffin (a mixture of C20-C40 saturated hydrocarbons, the same shall apply hereinafter) as the fluorine-free organic compound in CF3OCF(CF3)CF2OCF(CF3)COOH as the fluorine-containing organic acid (paraffin concentration in the whole of the solution: 25 mass-ppm), and then the fluorine-containing organic acid phase was taken out from the mixture to obtain a fluorine-containing organic acid solution 1. With respect to the fluorine-containing organic acid solution 1 obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured as 7.2 mass-ppm, and the concentration of water was 200 mass-ppm, and the concentration of sulfuric acid was 1200 mass-ppm.
    • Example 1
  • 50 g of concentrated sulfuric acid having a concentration of 90 mass% (water of 10 mass%) was added to 100 g of the fluorine-containing organic acid solution 1 (paraffin concentration: 7.2 mass-ppm) prepared in Production Example 1, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured. The result is shown in Table 1.
    • Example 2
  • 50 g of concentrated sulfuric acid having a concentration of 92 mass% (water of 8 mass%) was added to 100 g of the fluorine-containing organic acid solution 1 (paraffin concentration: 7.2 mass-ppm) prepared in Production Example 1, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured. The result is shown in Table 1.
    • Example 3
  • 50 g of concentrated sulfuric acid having a concentration of 94 mass% (water of 6 mass%) was added to 100 g of the fluorine-containing organic acid solution 1 (paraffin concentration: 7.2 mass-ppm) prepared in Production Example 1, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured. The result is shown in Table 1.
    • Example 4
  • 50 g of concentrated sulfuric acid having a concentration of 96 mass% (water of 4 mass%) was added to 100 g of the fluorine-containing organic acid solution 1 (paraffin concentration: 7.2 mass-ppm) prepared in Production Example 1, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured. The result is shown in Table 1.
    • Example 5
  • 50 g of concentrated sulfuric acid having a concentration of 98 mass% (water of 2 mass%) was added to 100 g of the fluorine-containing organic acid solution 1 (paraffin concentration: 7.2 mass-ppm) prepared in Production Example 1, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured. The result is shown in Table 1.
    • Production Example 2
  • 50 g of concentrated sulfuric acid having a concentration of 90 mass% (water of 10 mass%) was added to 100 g of a solution containing succinic acid as the fluorine-free organic compound in CF3OCF(CF3)CF2OCF(CF3)COOH as the fluorine-containing organic acid (succinic acid concentration in the whole of the solution: 25 ppm by mass), and then the fluorine-containing organic acid phase was taken out from the mixture to obtain a fluorine-containing organic acid solution 2. With respect to the fluorine-containing organic acid solution 2 obtained by this way, the concentration of succinic acid as the fluorine-free organic compound was measured as 4.3 mass-ppm, and the concentration of water was 200 mass-ppm, and the concentration of sulfuric acid was 1200 mass-ppm.
    • Example 6
  • 50 g of concentrated sulfuric acid having a concentration of 98 mass% (water of 2 mass%) was added to 100 g of the fluorine-containing organic acid solution 2 (succinic acid concentration: 4.3 mass-ppm) prepared in Production Example 2, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of succinic acid as the fluorine-free organic compound was measured. The result is shown in Table 1.
    • Production Example 3
  • 50 g of concentrated sulfuric acid having a concentration of 90 mass% (water of 10 mass%) was added to 100 g of a solution containing oxalic acid as the fluorine-free organic compound in CF3OCF(CF3)CF2OCF(CF3)COOH as the fluorine-containing organic acid (oxalic acid concentration in the whole of the solution: 25 mass-ppm), and then the fluorine-containing organic acid phase was taken out from the mixture to obtain a fluorine-containing organic acid solution 3. With respect to the fluorine-containing organic acid solution 3 obtained by this way, the concentration of oxalic acid as the fluorine-free organic compound was measured as 2.8 mass-ppm, and the concentration of water was 200 mass-ppm, and the concentration of sulfuric acid was 1200 mass-ppm.
    • Example 7
  • 50 g of concentrated sulfuric acid having a concentration of 98 mass% (water of 2 mass%) was added to 100 g of the fluorine-containing organic acid solution 3 (oxalic acid concentration: 2.8 mass-ppm) prepared in Production Example 3, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of oxalic acid as the fluorine-free organic compound was measured. The result is shown in Table 1.
    • Production Example 4
  • 50 g of concentrated sulfuric acid having a concentration of 90 mass% (water of 10 mass%) was added to 100 g of a solution containing citric acid as the fluorine-free organic compound in CF3OCF(CF3)CF2OCF(CF3)COOH as the fluorine-containing organic acid (citric acid concentration in the whole of the solution: 25 mass-ppm), and then the fluorine-containing organic acid phase was taken out from the mixture to obtain a fluorine-containing organic acid solution 4. With respect to the fluorine-containing organic acid solution 4 obtained by this way, the concentration of citric acid as the fluorine-free organic compound was measured as 9.8 mass-ppm, and the concentration of water was 200 mass-ppm, and the concentration of sulfuric acid was mass-1200 ppm.
    • Example 8
  • 50 g of concentrated sulfuric acid having a concentration of 98 mass% (water of 2 mass%) was added to 100 g of the fluorine-containing organic acid solution 4 (citric acid concentration: 9.8 mass-ppm) prepared in Production Example 4, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of citric acid as the fluorine-free organic compound was measured. The result is shown in Table 1. Table 1
    Fluorine-free organic compound Concentrated sulfuric acid phase ( mass%) Concentration of Fluorine-free organic compound (mass-ppm)
    Sulfuric acid Water
    Example 1 paraffin 90 10 0.9
    Example 2 paraffin 92 8 0.09
    Example 3 paraffin 94 6 0.06
    Example 4 paraffin 96 4 0.02
    Example 5 paraffin 98 2 ≤ 0.01
    Example 6 succinic acid 98 2 ≤ 0.1
    Example 7 oxalic acid 98 2 ≤ 0.1
    Example 8 citric acid 98 2 ≤ 0.1
    • Production Example 5
  • 50 g of concentrated sulfuric acid having a concentration of 90 mass% (water of 10 mass%) was added to 100 g of a solution containing paraffin (a mixture of saturated C20-40-hydrocarbons, the same shall apply hereinafter) as the fluorine-free organic compound in C5F11COOH as the fluorine-containing organic acid (paraffin concentration in the whole of the solution: 25 ppm by mass), and then the fluorine-containing organic acid phase was taken out from the mixture to obtain a fluorine-containing organic acid solution 5. With respect to the fluorine-containing organic acid solution 5 obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured as 5.5 mass-ppm, and the concentration of water was 450 mass-ppm, and the concentration of sulfuric acid was 4000 mass-ppm.
    • Example 9
  • 50 g of concentrated sulfuric acid having a concentration of 98 mass% (water of 2 mass%) was added to 100 g of the fluorine-containing organic acid solution 5 (paraffin concentration: 5.5 mass-ppm) prepared in Production Example 5, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured. The result is shown in Table 2.
    • Production Example 6
  • 50 g of concentrated sulfuric acid having a concentration of 90 mass% (water of 10 mass%) was added to 100 g of a solution containing paraffin (a mixture of saturated C20-40-hydrocarbons, the same shall apply hereinafter) as the fluorine-free organic compound in C3F7OCF(CF3)COOH as the fluorine-containing organic acid (paraffin concentration in the whole of the solution: 25 mass-ppm), and then the fluorine-containing organic acid phase was taken out from the mixture to obtain a fluorine-containing organic acid solution 6. With respect to the fluorine-containing organic acid solution 6 obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured as 6.3 mass-ppm, and the concentration of water was 900 mass-ppm, and the concentration of sulfuric acid was 3200 mass-ppm.
    • Example 10
  • 50 g of concentrated sulfuric acid having a concentration of 98 mass% (water of 2 mass%) was added to 100 g of the fluorine-containing organic acid solution 6 (paraffin concentration: 6.3 mass-ppm) prepared in Production Example 6, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured. The result is shown in Table 2.
    • Production Example 7
  • 50 g of concentrated sulfuric acid having a concentration of 90 mass% (water of 10 mass%) was added to 100 g of a solution containing paraffin (a mixture of saturated C20-40-hydrocarbons, the same shall apply hereinafter) as the fluorine-free organic compound in C3F7OCF(CF3)CF2OCF(CF3)COOH as the fluorine-containing organic acid (paraffin concentration in the whole of the solution: 25 mass-ppm), and then the fluorine-containing organic acid phase was taken out from the mixture to obtain a fluorine-containing organic acid solution 7. With respect to the fluorine-containing organic acid solution 7 obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured as 11.2 mass-ppm, and the concentration of water was 250 mass-ppm, and the concentration of sulfuric acid was 1600 mass-ppm.
    • Example 11
  • 50 g of concentrated sulfuric acid having a concentration of 98 mass% (water of 2 mass%) was added to 100 g of the fluorine-containing organic acid solution 7 (paraffin concentration: 11.2 mass-ppm) prepared in Production Example 7, and then the fluorine-containing organic acid phase was taken out from the mixture. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of paraffin as the fluorine-free organic compound was measured. The result is shown in Table 2. Table 2
    Fluorine-free organic compound Concentrated sulfuric acid phase ( mass%) Concentration of Fluorine-free organic compound (mass-ppm)
    Sulfuric acid Water
    Example 9 paraffin 98 2 ≤ 0.01
    Example 10 paraffin 98 2 ≤ 0.01
    Example 11 paraffin 98 2 ≤ 0.01
    • Example 12
  • 1000 g of the fluorine-containing organic acid solution 1' (paraffin concentration of 7.0 mass-ppm) prepared in the same manner as in Production Example 1 was passed from the supply port 11 of Fig. 1 (a) and 500 g of a concentrated sulfuric acid having a concentration of 90 mass% (10 mass% of water) was passed from the supply port 12 of Fig. 1 (a), and these were mixed by the static mixer 10. Thus mixed solution of them was discharged from the discharge port 14 of Fig. 1 (a), and then supplied to the liquid-liquid separation column 20. The mixed liquid supplied from the supply port 23 was left to stand and separated in the liquid-liquid separation column 20, and the fluorine-containing organic acid phase was taken out from the light liquid 22. With respect to the fluorine-containing organic acid phase obtained by this way, the concentration of paraffin was measured as ≤ 0.01 mass-ppm.
    • Industrial Applicability
  • The present method for purifying a C2-20-FOAcan be suitably used as a method for producing a C2-20-FOA, in particular fluorocarboxylic acid, in which the fluorine-free organic compound is reduced.
    • Reference Signs List
    • 10
    static mixer
    11, 12, 23, 32
    supply port
    13
    element
    14
    discharge port
    20
    liquid-liquid separation column
    21
    heavy liquid
    22
    light liquid
    30
    Karr column
    31
    cylindrical part
    33, 34
    tank part
    35
    extraction zone
    36
    lower end of cylindrical part
    37
    upper end of cylindrical part

Claims (6)

  1. A method for purifying a fluorine-containing C2-20-organic acid (A), comprising
    - contacting a mixture containing an acid (A) and a fluorine-free organic compound (B) with concentrated sulfuric acid and then
    - separating an acid (A) phase from a concentrated sulfuric acid phase,
    wherein
    - the acid (A) is selected from C2-20-fluorocarboxylic acids, C2-20-fluorosulfonic acids, and salts thereof,
    - the contacting is conducted such that an amount of water present in the concentrated sulfuric acid phase is ≤ 10 mass-%, and
    - the acid (A) is obtained in form of the acid (A) phase having a reduced content ratio of the compound (B) compared with the mixture.
  2. The method of claim 1, wherein the compound (B) has 1-50 carbon atoms.
  3. The method of claim 2, wherein the compound (B) comprises at least one of a C1-50-carboxylic acid and derivative thereof, a C8-50-hydrocarbon, a C6-50-phenol, a C1-30-alcohol, a C8-50-polyether and a C10-20-alkyl group-containing ionic compound.
  4. The method of any of claims 1-3, wherein the acid (A) is a C2-20-fluorocarboxylic acid or a salt thereof.
  5. The method of any of claims 1-4, wherein the mixture containing the acid (A) and the compound (B) is previously subjected to dehydration treatment.
  6. The method of claim 5, wherein the dehydration treatment is carried out by washing the mixture containing the acid (A) and the compound (B) with a sulfuric acid aqueous solution having a sulfuric acid concentration of ≥ 70 mass-%.
EP17813230.4A 2016-06-16 2017-06-09 Method of purifying a fluorinated c2-c20 organic acid Active EP3473610B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016119807 2016-06-16
PCT/JP2017/021478 WO2017217333A1 (en) 2016-06-16 2017-06-09 Method of producing c2–c20 fluorine-containing organic acid, and composition containing c2–c20 fluorine-containing organic acid

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EP3473610A1 EP3473610A1 (en) 2019-04-24
EP3473610A4 EP3473610A4 (en) 2020-02-12
EP3473610B1 true EP3473610B1 (en) 2023-07-19

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EP (1) EP3473610B1 (en)
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WO (1) WO2017217333A1 (en)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2903981A1 (en) * 1979-02-02 1980-08-07 Hoechst Ag RECOVERY OF FLUORINATED EMULGATOR ACIDS FROM BASIC ANION EXCHANGERS
DE3606174A1 (en) * 1986-02-26 1987-08-27 Hoechst Ag METHOD FOR PRODUCING PERFLUORIC CARBONIC ACIDS
DE4213154C1 (en) * 1992-04-22 1993-06-17 Hoechst Ag, 6230 Frankfurt, De
US6281374B1 (en) * 2000-08-23 2001-08-28 E. I. Du Pont De Nemours And Company Fluorinated alkanoic acid purification process
AU2003299137A1 (en) * 2002-09-16 2004-04-23 Texas Tech University System Inhibition of metallo-beta-lactamase
EP1542957B9 (en) * 2002-09-25 2009-10-28 E.I. Du Pont De Nemours And Company Process for preparing fluorocarboxylic acids
AU2003276878A1 (en) * 2002-09-30 2004-04-23 Daikin Industries, Ltd. Process for preparing fluorocarboxylic acids
JP4904761B2 (en) * 2005-09-30 2012-03-28 ユニマテック株式会社 Method for recovering fluorinated carboxylic acid
JP5347851B2 (en) 2008-09-08 2013-11-20 ダイキン工業株式会社 Method for producing fluorocarboxylic acid

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US10759731B2 (en) 2020-09-01
JP6795033B2 (en) 2020-12-02
EP3473610A1 (en) 2019-04-24
US20190330135A1 (en) 2019-10-31
CN109311796B (en) 2022-03-22
JPWO2017217333A1 (en) 2018-11-29
WO2017217333A1 (en) 2017-12-21
CN109311796A (en) 2019-02-05
EP3473610A4 (en) 2020-02-12

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